JPS58104927A - Preparation of anionic exchange membrane - Google Patents

Abstract

PURPOSE:To obtain an anionic exchange membrane with a low content of impurities suitable for regenerating a stable color developing solution, by treating an anionic exchange membrane containing quaternary ammonium groups with a nitrate. CONSTITUTION:An anionic exchange membrane containing quaternary ammonium groups, e.g. total four H atoms in ammonium ions are substituted by alkyl groups, e.g. methyl groups, is dipped in an aqueous solution of a nitrate, e.g. nitic acid or lithium nitrate, preferably in 0.2-2.0 N concentration, particularly at 10-40 deg.C, and repeatedly washed several times to give the aimed anionic exchange membrane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing an anion exchange membrane having five primary ammonium groups, and particularly provides an anion exchange membrane suitable for regenerating a color developer.

Today, anion exchange membranes are widely used in electrodialysis, diffusion dialysis, electrolysis membranes, etc. However, when a color developer is regenerated using a limited ion exchange membrane obtained by a conventional manufacturing method, a phenomenon is observed in which the sensitivity and fog values vary greatly when color development is performed using the developer. It was done.

In order to eliminate this phenomenon, attempts have been made to wash the anion exchange membrane with a solvent and then with seawater, but both methods have been insufficient.

As a result of repeated research in order to eliminate the above-mentioned disadvantages, the present inventors have learned that it is necessary to remove some impurities present in the anion exchange membrane.

Although this impurity has not yet been fully identified, the present invention was achieved based on the finding that the impurity can be easily removed by washing the anion exchange membrane with an aqueous nitrate solution.

Therefore, an object of the present invention is to provide an anion exchange membrane with a lower content of impurities, and another object is to provide an anion exchange membrane that can also be used for regenerating color developers. It is another object of the present invention to provide a method for regenerating stable nine-color fire fluid using an ion exchange membrane.

This object of the present invention is achieved by a method for producing an anion exchange membrane, which is characterized in that an anion exchange membrane having primary ammonium groups is treated with a nitrate.

The term "grade ammonium group" as used in the present invention includes ammonium ions in which all hydrogen atoms are substituted with alkyl groups, and examples of alkyl groups include methyl, ethyl, benzyl, ethanol, and the like. Primary ammonium groups include pyridinium bases such as methylpyridinium, ethylpyridinium, and benzylpyridinium.

The anion exchange membrane used in the present invention may be of any known type as long as it has a primary ammonium group. Typical examples of such known anion exchange membranes are as follows. Special public Akira Jt.
The so-called impregnated astringency seen in -13ri No. 0, Special Publication No. 37-117 De No. 0, etc.; Special Publication No. 117-77 Octopus, Special Publication No. 31-J! rri No. 3,
Special public Show 3 Deichi 15Fj4CJ, Special public Show 3 Taichi core 14
The so-called 12-stroke Shiburai, 1111 Special Public Sho 3 Co-Issan No. #J, Special Public Sho J--San no μ...: No. 1, etc. The so-called bulk polymerization observed in
-Dream! Styrene-butadiene copolymerizers found in No. 20, Tokko Sho//#jt, etc., polymer
8ci,,ko3. Examples of nitrates used in the present invention include nitric acid, lithium nitrate, sodium nitrate, potassium nitrate, ammonium nitrate, and silver nitrate. , hydrazine nitrate, calcium nitrate, magnesium nitrate, iron nitrate, nickel nitrate, zinc nitrate, cobalt nitrate, strontium nitrate, steel nitrate, manganese nitrate, barium nitrate, aluminum nitrate, etc., and any salt containing a nitrate group can be used. good.

These salts may be used in appropriate combinations, and may also be used in combination with other salts such as hydrochlorides, nitrates, perchlorates, sulfites, carbonates, and the like. Furthermore, it may be used in combination with the following buffer solutions. For example, boric acid-potassium chloride:mu-sodium hydroxide St, glycine-natobarium chloride-sodium hydroxide solution, sodium borate-sodium carbonate solution, hydrogen phosphate-sodium-potassium carbonate solution, sodium hydrogen carbonate-potassium carbonate solution, dimethyl glycine,
Various solutions described in the "Buffer Solutions" section of the Basic Chemistry Handbook, such as cinnamate, lithium-hydrochloric acid solution, boric acid + sodium chloride-sodium carbonate solution, sodium tetraborate-sodium chloride-boric acid solution, etc., can be used in combination.

As a treatment method, the anion exchange membrane is generally washed with a nitrate aqueous solution. For example, it may be simply immersed in the nitrate aqueous solution, but if the cleaning effect is not sufficient, it may be washed several times with a fresh nitrate aqueous solution. It is preferable to wash the ion exchange membrane while countercurrently flowing the nitrate aqueous solution thereto. The concentration of the cleaning solution is usually O, i~J, preferably O, J~, O, as the concentration of nitrate radicals. The temperature of the cleaning solution should be within a temperature range that does not degrade the performance of the anion exchange membrane, i.e. 0c or less, usually j6c or more and 4o''.
C or less, preferably from to''c to 300C or less.

For example, in the case of cleaning by immersion method, the cleaning time is usually 1 minute to 100 hours.

Although the cause of the effectiveness of the anion exchange membrane of the present invention is not yet clear, the inventors believe that it is effective for the following reasons. Because it is extremely large compared to ions, it can effectively remove minute amounts of impurities within the ion exchange membrane.

■ Since the nitrate radical itself is extremely stable, it will not have any adverse effects under the conditions of use.

■ Because nitrate radicals are inorganic, small-radius anions, they do not cause the organic contamination of anion exchange membranes that occurs with large organic anions.

When color processing is performed using a color developer regenerated using the ion exchange membrane manufactured using the present invention,
Variations in the sensitivity and fog of the processing agent photosensitive material can be reduced to #1, making it possible to obtain a product of almost constant quality, which is extremely advantageous in terms of quality control.

The color developing solution regenerated using the porous ion-exchange membrane obtained using the present invention may be prepared using a known -grade aromatic amine developer, such as phenylene cyanide (e.g.
. N-diethylaniline, 3-methyl-3-a2-no-N
, N-diethylaniline, l-ano-N-ethyl-N
-β-Hydroxyethylaniline, J-Methyl-Sen-Aguino-N-Ethyl-N-β-Citroxyethylaniline, 3-Methyl-Sen-Amino-N-ethyl-N-β-methanesulfamide ethylaniline, φ -Aζ)-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.).

Others L, F, A1Mason@Photograp
hicprocess mung Chemistry
(Published by Focal Press, 1944), pages J6-J, U.S. Patent Co., Ltd. J, No. 011, λ
,! It may include those described in Tako, No. 74, JP-A No. 441-33, and the like.

Color iJ! Our solutions contain #1 or #7 9H buffers such as potassium metal sulfites, carbonates, borates and phosphates;
3JL inhibitors or anti-capri agents such as bromides, iodides and organic anti-capri agents can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as indyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammomol salts, and amines, dye-forming couplers, and competitive couplers may also be used. , a fogging agent such as sodium borohydride! - Auxiliary developers such as phenyl-3-pyrazolidone, viscosity-imparting agents, US patents, Or! , the polycarboxylic acid chelating agent described in No. 721, West German Open
8) The antioxidant described in J, 4 here, RI No. 10, etc. may be included.

Example number average molecular weight Kota, Ko4/(measured by Gelper resistance knee chromatography), density O, De1711/38,
A polyethylene film with a thickness of JOOμ was exposed to a 100KeV electron beam accelerator at a dose rate of O6j megarads/sec.
□! Check out the electron beam dose! Irradiate it so that it becomes mega rad,
After crosslinking the polyethylene film, methacrylic acid-2
The sample was immersed in a monomer mixture containing -N,N-dimethylazunoethyl and vinylbenzyl iodide at a molar ratio of /'41 to impregnate the monomer. Next, this monomer-impregnated film was placed in a stainless steel container (the thickness of the stainless steel plate was 2 m/m), the air inside was replaced with nitrogen gas, the container was sealed, and the container was irradiated with ultraviolet rays to perform graft copolymerization. .

This film was taken out and washed with a sulfuric acid aqueous solution.
Homopolymers, copolymers, etc. that did not undergo graft polymerization were removed and dried. The grafting rate of the graft membrane after drying is sr
s, and the anion exchange capacity is 1. ? A strongly basic Ω anion exchange membrane of meq/l-dried resin membrane was obtained.

\ Plane using this breast ion exchange membrane (7)! Install the electrodialysis tank (1) as shown in the figure and use the following sensitive material and processing agent to regenerate the color solution.9.

1 Electrodialysis tank 2 Node 3 Anode 4 Cathode chamber i Anode chamber/agitation blade 7 #5 Ion exchange membrane Anode chamber and cathode chamber are both in the back Partitioned by an anion exchange membrane 1ooaa2 with monovalent ion selectivity in terms of volume/l It is being

For electrolysis, a carbon plate was used as an anode and a stainless steel plate was used as a cathode.

On a polyethylene-coated paper support, a layer of a blue-sensitive chlorobromide emulsion containing a yellow coupler emulsion dispersion, a green-sensitive silver chlorobromide emulsion containing a magenta coupler emulsion dispersion (silver chloride 7
Color Eaper was manufactured by coating a θ mole-) layer, a red-sensitive silver chlorobromide emulsion (silver chloride 70 mole-) layer containing a cyan coupler emulsion dispersion, and a -V futin layer containing an ultraviolet absorber. .

As a coupler, α-(J, Dazio Yaso!.

! /non-methyloxazolidinyl)-α-piparoyl-
λ-Kuroro! -((α-(co, di-t-amylphenoxy)butyl oxide I acetanilide,'(co,a,4-)lichlorophenyl)J-((λ-chloroJ-tetradecanado)anilino) -Copyrazolone-!-one and Hiko-i (!-(J, 3-di-t-amylphenoxy)-phthanado)-3,1-di-t-amylphenol!-methylphenol were used, respectively.

In addition, as ultraviolet absorbers, N, N/-di (hydroxy-1-anilino)-/, J, j-) riazine-coyl j-$, z/-cya-based nostilbeneco, co'-
Sodium disulfonate was used.

The coating amounts of coupler and silver salt for this color paper are as follows.

Exposure to this Color E 22 using a sensitometer (1 second j00c
M8) was given and the latter process was performed.

Coloring fA liquid benzyl alcohol / #sulfite-resistant sodium col potassium bromide
0. ! f Sodium carbonate (l water salt I JOf color developing agent '11
st hydroxylamine sulfate
2. If add water
/14k San-1 Den-N-ethyl-N-(β-methanesulfonamide)-m-)luidine (sesquisulfate monohydrate: Bleach-fix ammonium thiosulfate tzog1z Sodium sulfite llNa (Fe
l(EDTA))
Add 11 tatami mats of water and ethylenediaminetetraacetic acid anodized sodium carbonate (l hydrated salt) If sodium bicarbonate Potassium bromide Add sulfuric acid
P) it, add water to make j
/1 Strips (A: type) treated with a newly made copper color developing solution having the above composition, Color Eaper 4L4M"2 o l Oh 5-i my fi
Strips (B) treated with the solution (solution B) after the temm filling treatment and the nine anion exchange membrane prepared by the method described above were immersed in a solution with the following composition (cleaning solution) for 10 minutes, and the process was repeated twice. Three strips (C) were compared, which were treated with a solution obtained by regenerating the solution of B by electrodialysis using an exchange membrane that had been washed by the same method.

Cleaning solution (C) Trisodium nitrilotriacetate / I/1 sodium nitrate 3o1/1 salt J
θf/1 Furthermore, as a comparative example of the cleaning method, the one treated with water for 2 weeks (
D), one that was immersed and washed day and night in seawater (E), one that was washed for a week with a solution of Glauber's salt (JOf/L), (F), assembled in a dialysis tank and dripped with seawater, and then the ion exchange membrane 73. JF
Solution B was regenerated using IA/day/night processed material (G) and its photographic properties were checked.

As an example of other cleaning liquids included in the present invention, an anion exchange membrane prepared by the method described above using the following H-I cleaning liquid was
The B solution was regenerated using an exchange membrane that had been soaked for 1 minute and then washed once, and its photographic properties were checked.

Cleaning liquid (H) KNOs HiroOf/IN a 2
COs / Of / 1 Cleaning liquid (I) N a N Os J z f
/1 As is clear from Table 1, when an anion exchange membrane treated using a conventionally known cleaning method is used, the sensitivity of the photosensitive material increases and it is difficult to obtain a constant sensitivity. Furthermore, the capri is increased. On the other hand, when using an anion exchange membrane treated by the method of the present invention, almost the same photographic properties can be obtained as when using a freshly prepared existing solution.

Claims (1)

[Claims] /) A method for producing a breast ion exchange membrane, which comprises treating an anion exchange membrane having a primary ammonium group with a nitrate.